CN101423758A - Method for preparing white light quantum point - Google Patents
Method for preparing white light quantum point Download PDFInfo
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- CN101423758A CN101423758A CNA2007101659340A CN200710165934A CN101423758A CN 101423758 A CN101423758 A CN 101423758A CN A2007101659340 A CNA2007101659340 A CN A2007101659340A CN 200710165934 A CN200710165934 A CN 200710165934A CN 101423758 A CN101423758 A CN 101423758A
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Abstract
The invention provides a method for preparing a quantum dot capable of emitting white light, wherein the quantum dot has a chemical formula of Zn1-xCdxA; A can be a mixture of S or S1-ySey; x is more than 0 and less than 1; and y is more than 0 and less than 1. The preparation method for the white-light quantum dot comprises the following steps of: (a) preparing a sulfur-containing organic solution; (b) dissolving a zinc-containing precursor and a cadmium-containing precursor in an organic acid and a cosolvent so as to prepare a homogeneous solution; and (c) mixing the sulfur-containing organic solution with the homogeneous solution so as to generate the white-light quantum dot of Zn1-xCdxA through reaction. As the preparation method for the Zn1-xCdxA quantum dot adopts a one-time synthesis mode, the preparation method is simple in preparation steps and can reduce manufacture cost. In addition, the prepared Zn1-xCdxA quantum dot has the wavelength range of emitted light between 400 and 800 nanometers.
Description
Technical field
The present invention relates to a kind of preparation method of quantum dot, particularly relates to a kind of preparation method who launches the quantum dot of white light.
Background technology
At present, the preparation method of fluorescent material has following several: high-temperature sintering process (sintering), sol-gel method (sol-gel), microwave heating method (micro-wave hyperthermia) etc.Wherein, high-temperature sintering process is as the term suggests promptly be by 1000 ℃ of high temperature (〉) diffusion between the promote the oxidation thing, to reach the purpose that forms compound.Yet,, therefore need reaction for a long time because the diffusion process between oxide compound is slow.And the sol-gel rule is to form earlier precursor (precursor) at low temperatures, then, this precursor is at high temperature carried out solid-state diffusion reaction (solid state diffusional reaction), to make fluorescent material, so belong to the secondary processing procedure.In addition, the microwave heating rule is to be heating source with the microwave, utilizes microwave to have the characteristic of local fast heating, carries out the solid-state diffusion reaction.Yet above-mentioned preparation method only can prepare the monochromatic fluorescent material of emission.In the conventional fluorescent powder,, can adjust the emission wavelength of fluorescent material by doping different activities element because crystal field (lattice filed) effect is different with electronic cloud (electron cloud) expansible effect.Yet,, make these fluorescent material only can be excited, and its power loss is bigger at some optical excitation wave band because the energy that the luminescence mechanism of fluorescent material belongs between molecular orbital(MO) (different track f-d, or same rail f-f) shifts.
Generally speaking, fluorescent material is mainly used in colour developing, and it is promptly luminous to anticipate.For example, in having the photodiode of energy conservation characteristic, fluorescent material more obtains to use widely.Because fossil energy peters out, make photodiode potentialization, particularly white light emitting diode more in the application of illumination with energy conservation characteristic.
The mode of making white light emitting diode at present mainly contains two classes: one is many grain types lumination of light emitting diode mode, is about to three kinds of crystal grain of red, green, blue and encapsulates simultaneously, and then these three primary colors can blend together white light; One is single die type lumination of light emitting diode mode, promptly utilize the single LED crystal particle fluorescent material of all kinds of arranging in pairs or groups to blend together white light, the method of using mainly is to utilize blue light-emitting diode crystal grain and gold-tinted fluorescent material (yttrium aluminium garnet fluorescent powder at present, abbreviation YAG fluorescent material) light that is sent is mixed into white light, or utilize ultraviolet light-emitting diodes crystal grain, excite blue light, green glow and red light fluorescent powder, make to be mixed into white light.
In addition, the mode of launching white light if use UV-light chip excitated fluorescent powder then needs to mix simultaneously indigo plant, green, red trichromatism fluorescent material, and the decline of these three kinds of fluorescent material is all inequality with its luminous efficiency, so has also increased the degree of difficulty of technology and design.
From the above, existing fluorescent material is all monochromatic ray at present, need mix two or more light if will obtain white light.Therefore, also increase white light and send out the cost of diode and the degree of difficulty of technology.
Therefore, need a kind of mixed light that do not need to launch novel material of white light and preparation method thereof, and above-mentioned preparation method not only can save the cost of manufacture of white light emitting diode, also can address the above problem simultaneously.
Summary of the invention
Therefore, one of the present invention purpose provides a kind of preparation method of white light quanta point.Above-mentioned white light quanta point has Zn
1-xCd
xThe chemical formula of A, and A can be the mixture of S or itself and Se, and 0＜x＜1.For example be Zn
1-xCd
xAmong the embodiment of S quantum dot, its preparation method comprises: (a) preparation one sulfur-containing organic solution; (b) contain zinc precursor thing and with one and contain the cadmium precursor and mix in an organic acid, to prepare a huge legendary turtle compound, this huge legendary turtle compound is dissolved among the cosolvent (co-solvent) again, promptly makes a homogeneous (homogeneous) solution; And (c) mix above-mentioned sulfur-containing organic solution and homogeneous solution, generate Zn with reaction
1-xCd
xThe white light quanta point of S (white light quantum dot).Because above-mentioned Zn
1-xCd
xThe preparation method of S quantum dot prepares in a synthetic mode.Therefore, preparation process is comparatively simple and easy, and can reduce its cost of manufacture.In addition, at above-mentioned Zn
1-xCd
xBe formed with an organic molecule on the surface of S quantum dot, and this organic molecule is to coat this Zn
1-xCd
xThe S quantum dot is avoided oxidation to protect this quantum dot, and is helped quantum dot to be dissolved among the organic solvent.
Moreover, via the prepared Zn of aforesaid method
1-xCd
xThe particle diameter of S quantum dot is less than 10 nanometers, or even less than 5 nanometers, therefore, also can be described as nanocrystal.Because this nanocrystal has the size of nano-scale (nano-scaling), makes it have quantum confinement effect (quantum confinement effect).Therefore, can improve the again composite efficiency of carrier in quantum dot, and then promote Zn
1-xCd
xThe luminous efficiency of S quantum dot.In addition, the above-mentioned Zn of optical excitation that is less than or equal to 450 nanometers by the optical excitation wavelength
1-xCd
xS quantum dot, but the white light of its emission wavelength ranges between 400～800 nanometers.
At above-mentioned A is among the embodiment of S and Se mixture, for example is Zn
1-xCd
xS
1-ySe
y(0＜y＜1), its preparation method more comprise mixes one with above-mentioned sulfur-containing organic solution and contains selenium organic solution, to make a sulfur-bearing and to contain the organic solution of selenium; And the organic solution of mixing this sulfur-bearing and containing selenium promptly makes a Zn in above-mentioned homogeneous solution
xCd
1-xS
1-ySe
yQuantum dot.This Zn
1-xCd
xS
1-ySe
yAfter the excitation of quantum dot by 365 nanometers or 400 nanometers, but emission wavelength ranges is between the white light of 400～700 nanometers.
Description of drawings
Fig. 1 is according to the prepared Zn of the embodiment of the invention
1-xCd
xThe synoptic diagram of S quantum dot (0＜x＜1);
Fig. 2 is the Zn of the embodiment of the invention 1
0.8Cd
0.2The transmission electron microscope photo of S quantum dot;
Fig. 3 is the Zn of the embodiment of the invention 1
0.8Cd
0.2The energy dispersed light spectrogram of S quantum dot;
Fig. 4 is the Zn of the embodiment of the invention 1
0.8Cd
0.2The X-ray diffraction chart of S quantum dot;
Fig. 5 is the Zn of the embodiment of the invention 1
0.8Cd
0.2The photoluminescence spectrogram of S quantum dot;
Fig. 6 is the prepared Zn of use amino dodecane of the embodiment of the invention 1
0.8Cd
0.2The transmission electron microscope photo of S quantum dot;
Fig. 7 is the prepared Zn of use amino dodecane of the embodiment of the invention 1
0.8Cd
0.2The photoluminescence spectrogram of S quantum dot;
Fig. 8 is the Zn of the embodiment of the invention 2
0.5Cd
0.5The transmission electron microscope photo of S quantum dot;
Fig. 9 is the Zn of the embodiment of the invention 2
0.5Cd
0.5The X-ray diffraction chart of S quantum dot;
Figure 10 is the Zn of the embodiment of the invention 2
0.5Cd
0.5The photoluminescence spectrogram of S quantum dot;
Figure 11 is the Zn of the embodiment of the invention 3
0.9Cd
0.1The transmission electron microscope photo of S quantum dot;
Figure 12 is the Zn of the embodiment of the invention 3
0.9Cd
0.1The photoluminescence spectrogram of S quantum dot;
Figure 13-14 is the prepared Zn of differential responses time of the embodiment of the invention 4
0.7Cd
0.3The photoluminescence spectrogram of S quantum dot;
Figure 15-16 is the prepared Zn of differential responses time of the embodiment of the invention 5
0.6Cd
0.4The photoluminescence spectrogram of S quantum dot; And
Figure 17 is the Zn of the embodiment of the invention 6
0.8Cd
0.2S
0.9Se
0.1The photoluminescence spectrogram of quantum dot.
Wherein, drawing reference numeral:
10～quantum dot;
20～organic molecule.
Embodiment
For above and other objects of the present invention, feature and advantage can be become apparent, cited below particularlyly go out preferred embodiment, and cooperate appended graphicly, be described in detail below:
Zn
0.8Cd
0.2The preparation of S quantum dot
At first, the 0.0481 sulphur powder that restrains (sulfur is called for short S) is placed vacuum environment, to remove adsorbed aqueous vapor in the sulphur powder.Then, in vacuum or be full of under the environment of noble gas, the organic solvent that adds for example vaccenic acid (octadecene) of 4 milliliters (ml), and be heated between 40 ℃～80 ℃, and through about 20～40 minutes of ultrasonic oscillation processing (ultrasonic shocking treatment), to make sulfur-containing organic solution (A liquid), for example be colourless vaccenic acid sulphur solution.When above-mentioned ultrasonic oscillation was handled, temperature is preferable can be 80 ℃, and concussion was handled about 30 minutes.It should be noted that, the organic solvent of above-mentioned vaccenic acid also can use other suitable phosphine lipid, tri octyl phosphine (tri-n-octyl phosphine for example, be called for short TOP) or tributylphosphine (tri-n-butylphosphine, be called for short TBP) or for example be the dioctylamine amine of (Dioctylamine is called for short DOA).In view of the above, above-mentioned sulfur-containing organic solution also can be tri octyl phosphine sulphur solution, tributylphosphine sulphur solution or dioctylamine sulphur solution.
In addition, with 0.0194 gram for example be zinc oxide (ZnO) powder contain zinc precursor thing (zinc precursor) and 0.0077 gram for example be Cadmium oxide (CdO) powder contain cadmium precursor (cadmium precursor), place in the three-necked bottle, and being full of for example is under the noble gas environment of argon gas, be heated to 120 ℃, and held temperature about 20 minutes, to remove the aqueous vapor of above-mentioned zinc oxide and Cadmium oxide.Afterwards, be cooled to room temperature.After cooling, then, add the organic acid of for example stearic acid (stearic acid is called for short SA) of 0.6828 gram, afterwards, be warming up to 230 ℃, to form the huge legendary turtle compound.Then, after reducing to room temperature, add the cetylamine (hexadecylamine is called for short HAD) of 5.82 grams and the trioctyl phosphine oxide (tri-n-octylphosphineoxide of 5.82 grams again, be called for short TOPO) in above-mentioned three-necked bottle, and stirred above-mentioned mixed powder about 5 minutes.Then, heat above-mentioned mixed powder to 320 ℃, to prepare a clarifying homogeneous solution (B liquid).
The above-mentioned zinc precursor thing that contains also can be to use zinc acetate (zinc acetate), Zinic stearas (zinc stearate) or zinc ethyl (diethyl zinc) to replace above-mentioned zinc oxide, also can be to use cadmium acetate (cadmium acetate) or dimethyl cadmium (dimethyl cadmium) to replace above-mentioned Cadmium oxide and contain the cadmium precursor.
In addition, above-mentioned stearic acid can be used as an intercalating agent, and also can use other appropriate organic to replace, and for example is lauric acid (lauric acid) or oleic acid (oleic acid).And above-mentioned cetylamine and trioctyl phosphine oxide also can be referred to as cosolvent (co-solvent), and the reaction reagent of above-mentioned cetylamine also can use other suitable organic amine to replace, for example amino dodecane (dodecylamine is called for short DDA).
At above-mentioned huge legendary turtle compound, add cetylamine and trioctyl phosphine oxide and be warming up to 320 ℃ become clarification homogeneous solution (B liquid) after, then, in above-mentioned sulfur-containing organic solution (A liquid) adding three-necked bottle.Between 250 ℃～350 ℃, preferred range was reacted above-mentioned sulfur-containing organic solution and homogeneous solution about 1 second～120 minutes between 285 ℃～295 ℃, can make Zn in temperature range
0.8Cd
0.2The nanocrystal of S quantum dot.
It should be noted that before adding A liquid the purpose of heating B liquid to 320 ℃ mainly is when avoiding adding A liquid (being lower than the temperature of B liquid), can reduce the temperature of reaction of whole mixing solutions (A liquid and B liquid).Therefore, before mixing A liquid and B liquid, the temperature of heating B liquid can be greater than 320 ℃ or less than 320 ℃.In addition, the temperature of reaction behind above-mentioned mixing A liquid and the B liquid is preferable can be about 290 ℃, and holds temperature about 60 minutes.
Fig. 1 shows the synoptic diagram according to nanocrystal of the present invention and the formed structure of organic molecule.In Fig. 1, can find Zn
0.8Cd
0.2The quantum dot 10 of S is coated by the organic molecule 20 that for example is trioctyl phosphine oxide, makes to protect Zn
0.8Cd
0.2The S quantum dot is avoided oxidation, and easier being dissolved among the organic solvent.Moreover, what deserves to be mentioned is that above-mentioned organic molecule 20 is to utilize the mode of bond to be formed on the surface of quantum dot 10.
In addition, above-mentioned prepared Zn
0.8Cd
0.2The particle diameter of S quantum dot is preferably less than 5 nanometers (nm) less than 10 nanometers (nm).Because this nanocrystal has the size of nano-scale (nano-scaling), makes it have quantum confinement effect (quantum confinement effect).Therefore, carrier (carrier) compound again (recombination) efficient in quantum dot is improved.So the nanocrystal of the embodiment of the invention 1 has higher relatively luminous efficiency.
Preparing above-mentioned Zn
0.8Cd
0.2After the S quantum dot.Then, can utilize the hot methanol purifying after, and again with Zn
0.8Cd
0.2The S quantum dot is dissolved in the hexane solution, to treat follow-up authentication step.
Zn
0.8Cd
0.2The evaluation of S
Finish above-mentioned Zn
0.8Cd
0.2After the preparation of S quantum dot, then, utilize energy scatter spectra (EnergyDispersive Spectrometer, abbreviation EDS), X-ray diffractometer (X-Ray Diffraction Meter, abbreviation XDR), transmission electron microscope (Transmission Electron Microcopy, be called for short TEM) and photoluminescence spectrogram (photoluminescence spectrum is called for short PL) identify the character of this sample.
Fig. 2 demonstration utilizes transmission electron microscope to take above-mentioned Zn
0.8Cd
0.2The photo of S quantum dot gained.As shown in Figure 2, can find above-mentioned prepared Zn
0.8Cd
0.2The particle diameter of S quantum dot is approximately less than 5 nanometers, and its each Zn
0.8Cd
0.2The size distribution of S quantum dot is very even.In addition, this image shows this Zn
0.8Cd
0.2The S quantum dot is a monocrystalline.Because this Zn
0.8Cd
0.2The S quantum dot has nano-scale, so also can be described as nanocrystal.
Fig. 3 shows above-mentioned Zn
0.8Cd
0.2The energy dispersed light spectrogram of S nanocrystal.The analytical results of energy dispersed light spectrogram thus, the sample of above-mentioned preparation except Zn, Cd and S element signal, has very strong P element signal simultaneously as can be known.Shown in Fig. 2,3, the sample of inferring above-mentioned preparation is one to comprise the ternary compound of Zn, Cd and S element, and more coats the organic molecule of trioctyl phosphine oxide on the surface of this sample.In addition, the signal of other elements such as Cu that shows at energy dispersed light spectrogram and C is the composition of plating carbon copper mesh in testing process, at this and no longer describe in detail.
Fig. 4 is above-mentioned Zn
0.8Cd
0.2The X-ray diffractogram of S quantum dot.The analytical results of X-ray diffractogram shows that above-mentioned prepared sample between pure ZnS and pure CdS, has diffraction peak thus.Infer that thus above-mentioned prepared structures of samples is the alloy between between ZnS and CdS.
Fig. 5 is Zn
0.8Cd
0.2The photoluminescence spectrogram of S quantum dot.In Fig. 5, be respectively with this Zn of optical excitation of wavelength 365 nanometers and 400 nanometers
0.8Cd
0.2The S quantum dot.Can find this Zn
0.8Cd
0.2The optical excitation light wavelength of S quantum dot is the white light between 400～750 nanometers.Therefore, the mode according to the embodiment of the invention 1 can make a white light quanta point.
According to above qualification result, use the mode of the embodiment of the invention 1 as can be known, can make Zn with emission white light
0.8Cd
0.2The S quantum dot.In addition, at this Zn
0.8Cd
0.2Form organic molecule on the surface of S quantum dot, and this organic molecule more coats this Zn
0.8Cd
0.2The nanocrystal of S.
In addition, Fig. 6 shows Zn
0.8Cd
0.2The transmission electron microscope photo of S quantum dot.Different with aforementioned preparation method is the Zn in Fig. 6
0.8Cd
0.2The S quantum dot is to use amino dodecane to replace the prepared Zn of cosolvent of cetylamine
0.8Cd
0.2The experimental example of S quantum dot.By shown in Figure 6, use the prepared Zn of amino dodecane as can be known
0.8Cd
0.2The particle diameter of S quantum dot is less than 3 nanometers, and this Zn
0.8Cd
0.2The S quantum dot has uniform size distribution.
Fig. 7 shows that the use amino dodecane is as the prepared Zn of cosolvent
0.8Cd
0.2The photoluminescence spectrogram of S quantum dot.Hence one can see that, uses amino dodecane as the prepared Zn of cosolvent
0.8Cd
0.2The emission wavelength of S quantum dot is between the white light of 400～750 nanometers.
Embodiment 2---Zn
0.5Cd
0.5The preparation of S quantum dot and evaluation
Zn
0.5Cd
0.5The preparation of S quantum dot
At first, the sulphur powder of getting 0.0481 gram places vacuum environment, to remove adsorbed aqueous vapor in the sulphur powder.Then, in vacuum or be full of under the environment of noble gas, add the organic solvent of 4 milliliters for example vaccenic acid, with the sulfur-containing organic solution (A liquid) of preparation example such as vaccenic acid sulphur.In embodiment 2, the preparation method of this sulfur-containing organic solution can be similar to embodiment 1, so no longer describe in detail at this.
Then, prepare a homogeneous solution (B liquid).In this embodiment, the preparation process of homogeneous solution is similar to embodiment 1.Therefore, only sketch the Zn of embodiment 2 at this
0.5Cd
0.5The preparation of S quantum dot.
At first, get the zinc oxide of 0.0122 gram and the Cadmium oxide of 0.0193 gram, be placed in the three-necked bottle, and be full of under the environment of noble gas, heat 120 ℃, to remove aqueous vapor about 20 minutes.Afterwards, reduce to room temperature.Then, add earlier the stearic acid of 0.6828 gram, and be warming up to 230 ℃, get final product a huge legendary turtle compound.Then, reduce to room temperature, the trioctyl phosphine oxides that add the cetylamines of 5.82 grams and 5.82 grams again are in three-necked bottle, and stir about 5 minutes.Then, be warming up to 320 ℃, to prepare a clarifying homogeneous solution (B liquid).
Afterwards, described as embodiment 1, above-mentioned vaccenic acid sulphur solution (A liquid) is added in the three-necked bottle, and under about 290 ℃ of temperature,, promptly make the Zn of embodiment 2 with about 1 minute of homogeneous solution (B liquid) reaction
0.5Cd
0.5The S quantum dot.This Zn
0.5Cd
0.5The surface of S quantum dot is to coat an organic molecule, avoids oxidation to protect this quantum dot.Moreover, Zn
0.5Cd
0.5The particle diameter of S quantum dot is less than 5 nanometers.
Scrutable is that the reaction reagent in embodiment 2 can certainly use embodiment 1 disclosed compound to replace.
Zn
0.5Cd
0.5The evaluation of S
Finish above-mentioned Zn
0.5Cd
0.5After the preparation of S quantum dot, then, with X-ray diffractometer (X-RayDiffraction Meter, abbreviation XDR), transmission electron microscope (Transmission ElectronMicrocopy, be called for short TEM) and photoluminescence spectrogram (photoluminescence spectrum is called for short PL) identify the character of this sample.
Fig. 8 takes above-mentioned Zn for utilizing transmission electron microscope
0.5Cd
0.5The photo of S quantum dot gained.As shown in Figure 8, can find above-mentioned prepared Zn
0.5Cd
0.5The particle diameter of S quantum dot is approximately less than 5 nanometers, and its each Zn
0.5Cd
0.5The size distribution of S quantum dot is very even.In addition, this image shows this Zn
0.5Cd
0.5The S quantum dot is a monocrystalline.Because this Zn
0.5Cd
0.5The S nanocrystal has nano-scale, makes to have quantum confinement effect (quantum confinement effect).Therefore, the Zn of the embodiment of the invention 2
0.5Cd
0.5The S nanocrystal has higher relatively luminous efficiency.
Fig. 9 is above-mentioned Zn
0.5Cd
0.5The X-ray diffractogram of S quantum dot.The analytical results of X-ray diffractogram shows that above-mentioned prepared sample between pure ZnS and pure CdS, has diffraction peak thus.Infer that thus above-mentioned prepared structures of samples is the alloy between between ZnS and CdS.Moreover, in Fig. 9, the diffraction peak of trioctyl phosphine oxide being arranged equally, it shows Zn
0.5Cd
0.5Be formed with the organic molecule of trioctyl phosphine oxide on the surface of S quantum dot, and this organic molecule more coats this quantum dot.
Figure 10 is Zn
0.5Cd
0.5The photoluminescence spectrogram of S quantum dot.In Figure 10, be respectively with this Zn of optical excitation of wavelength 365 nanometers and 400 nanometers
0.5Cd
0.5The S quantum dot.Can find this Zn
0.5Cd
0.5The optical excitation light wavelength of S quantum dot is the white light between 400～800 nanometers.Therefore, can make one according to the mode of the embodiment of the invention 2 and can launch the quantum dot of white light wavelength period.
More than comprehensive as can be known, according to the prepared Zn of the mode of embodiment 2
0.5Cd
0.5The surface of S quantum dot is to coat an organic molecule, and this Zn
0.5Cd
0.5The quantum dot of S can be launched white light.
According to the preparation method of embodiment 1, and the mol ratio between the allotment reaction reagent, with preparation Zn
0.9Cd
0.1The S quantum dot.Compare the foregoing description, among this embodiment 3, about 30 minutes of the reaction times of sulfur-containing organic solution and huge legendary turtle compound solution.That is to say, in this embodiment 3, under 290 ℃, mix sulfur-containing organic solution and huge legendary turtle compound solution, and hold about 30 minutes of temperature reaction.
Then, utilize transmission electron microscope (Transmission Electron Microcopy is called for short TEM) and photoluminescence spectrogram (photoluminescence spectrum is called for short PL) to identify the character of this sample.
Figure 11 shows the Zn of embodiment 3
0.9Cd
0.1The transmission electron microscope photo of S quantum dot.Can find above-mentioned prepared Zn
0.9Cd
0.1The particle diameter of S quantum dot is approximately less than 5 nanometers, and its each Zn
0.9Cd
0.1The size distribution of S quantum dot is very even.
Figure 12 is Zn
0.9Cd
0.1The photoluminescence spectrogram of S quantum dot.In Figure 12, be respectively with this Zn of optical excitation of wavelength 365 nanometers and 400 nanometers
0.9Cd
0.1The S quantum dot.Can find this Zn
0.9Cd
0.1The optical excitation light wavelength of S quantum dot is the white light between 400～800 nanometers.Therefore, can make one according to the mode of the embodiment of the invention 3 and can launch the quantum dot of white light wavelength period.
More than comprehensive as can be known, according to the prepared Zn of the mode of embodiment 3
0.9Cd
0.1The S quantum dot can be launched has the white light of containing about 400～800 nanometers of wavelength, and this Zn
0.9Cd
0.1The surface of S quantum dot is to coat an organic molecule.
Embodiment 4---Zn
0.7Cd
0.3The preparation of S quantum dot and evaluation
According to above-mentioned preparation process, different mol ratio between the allotment reaction reagent is with the Zn of preparation embodiment 4
0.7Cd
0.3The S quantum dot.And in this embodiment 4, prepare Zn with the different reaction times more respectively
0.7Cd
0.3The nanocrystal of S quantum dot.
In the reaction times is 5 minutes experimental example, above-mentioned sulfur-containing organic solution is mixed huge legendary turtle compound solution, and under about 290 ℃, reacted about 5 minutes, promptly make the Zn of first experimental example
0.7Cd
0.3(back claims Zn to the S quantum dot
0.7Cd
0.3The S-5 quantum dot).And, in the reaction times is 10 minutes experiment, after mixing above-mentioned sulfur-containing organic solution and huge legendary turtle compound solution, under 290 ℃, reacted about 10 minutes, promptly make the Zn of this second experimental example
0.7Cd
0.3(back claims Zn to the S quantum dot
0.7Cd
0.3The S-10 quantum dot).
Figure 13 shows the Zn of first experimental example of this embodiment 4
0.7Cd
0.3The photoluminescence spectrogram of S quantum dot.In Figure 13, be the Zn in the 5 minutes optical excitation reaction times of 365 nanometers with wavelength
0.7Cd
0.3The S quantum dot can be found Zn
0.7Cd
0.3The S-5 quantum dot can be launched the white light of wavelength region 400～800 nanometers.Figure 14 shows the Zn of second experimental example of this embodiment 4
0.7Cd
0.3The photoluminescence spectrogram of S quantum dot.In Figure 14, with wavelength respectively the Zn in the 10 minutes optical excitation reaction times of 365 nanometers and 400 nanometers
0.7Cd
0.3The S quantum dot can be found Zn
0.7Cd
0.3The S-10 quantum dot can be launched the white light of wavelength region 400～800 nanometers.
In view of the above, the prepared Zn of embodiment 4
0.7Cd
0.3But the S quantum dot is the white light of about 400～800 nanometers of emission wavelength ranges really.
According to the preparation process of the foregoing description 1, different mol ratio between the allotment reaction reagent is with the Zn of preparation embodiment 5
0.6Cd
0.4The S quantum dot.And in this embodiment 5, prepare Zn with the different reaction times more respectively
0.6Cd
0.4The nanocrystal of S quantum dot.
As embodiment 4, this embodiment 5 comprises that respectively the reaction times is the experimental example in 5 minutes and 10 minutes reaction times.Figure 15 shows the Zn in the 5 minutes reaction times of first experimental example among this embodiment 5
0.6Cd
0.4The photoluminescence spectrogram of S quantum dot.In Figure 15, be respectively with the Zn of optical excitation first experimental example of wavelength 365 nanometers and 400 nanometers
0.6Cd
0.4The S quantum dot can be found Zn
0.6Cd
0.4But S quantum dot emission wavelength ranges is between the white light of 400～800 nanometers.And, in Figure 16, with wavelength respectively the Zn in the 10 minutes optical excitation reaction times of 365 nanometers and 400 nanometers
0.6Cd
0.4The S quantum dot can be found Zn
0.6Cd
0.4The S quantum dot can be launched the white light of wavelength region 400～800 nanometers.
More than comprehensive, according to the prepared Zn of the embodiment of the invention
1-xCd
xS (0＜x＜1) but the quantum dot emission wavelength ranges between the visible light of 400～800 nanometers, and its particle diameter is more less than 10 nanometers.In addition, at Zn
1-xCd
xForm organic molecule on the surface of S quantum dot, and this organic molecule is to coat this amount idea, with protection Zn
1-xCd
xThe S quantum dot is avoided oxidation, and can with the organic solvent compatibility.Moreover above-mentioned preparation process (once synthetic) is comparatively simple, therefore, also can reduce preparation cost.
In addition, because Zn
1-xCd
xThe S quantum dot can be by the optical excitation less than 450 nanometers (UV-light), and Zn
1-xCd
xThe S quantum dot has broad exciting light wave band.Therefore, Zn
1-xCd
xThe S quantum dot can be used to replace the fluorescent material in the conventional white light diode.
Embodiment 6---Zn
0.8Cd
0.2S
0.9Se
0.1The preparation of quantum dot and evaluation
According to the mode of the foregoing description 1, also can prepare a nanocrystal with quad alloy.Compared to previous embodiment, maximum difference is the preparation of A liquid.
At first, the sulphur powder of 0.0433 gram being removed aqueous vapor adds in the organic solvent of 4 milliliters of vaccenic acids, and under 80 ℃ of the temperature, through a ultrasonic oscillation, with preparation vaccenic acid sulphur.In addition, the selenium (selenium is called for short Se) of 0.0118 gram being removed aqueous vapor is dissolved in the organic solvent of 0.2 milliliter of tri octyl phosphine and 0.8 ml n-hexane, and at room temperature, with ultrasonic oscillation, can obtain one and contain selenium organic solution.Afterwards, with above-mentioned sulfur-containing organic solution with contain selenium organic solution and mix, and a sulfur-bearing and contain the organic solution of selenium, i.e. A liquid.
Then, after preparation and the homogeneous solution (B liquid) of embodiment 1 similar mol ratio, this homogeneous solution is heated to 320 ℃.Afterwards, with A liquid mixing B liquid, and under 290 ℃, reacted about 10 minutes, to make Zn
0.8Cd
0.2S
0.9Se
0.1Quantum dot.
Scrutable is that the reaction reagent of present embodiment can certainly use embodiment 1 described reaction reagent.In addition, the homogeneous solution in the present embodiment (B liquid) can certainly be used the homogeneous solution of mol ratio similar to the aforementioned embodiment, and different mol ratio between sulphur and selenium in the allotment A liquid, with the quantum dot of the quad alloy for preparing various different ratioss.
Figure 17 shows Zn
0.8Cd
0.2S
0.9Se
0.1The photoluminescence spectrogram of quantum dot.In Figure 17, be respectively with the optical excitation Zn of wavelength 365 nanometers and 400 nanometers
0.8Cd
0.2S
0.9Se
0.1Quantum dot.Can find Zn
0.8Cd
0.2S
0.9Se
0.1But the quantum dot emission wavelength ranges is between the white light of 400～700 nanometers.
More than comprehensive, prepared quad alloy quantum in the present embodiment, it has a chemical formula: Zn
1-xCd
xS
1-ySey, and preferable 0＜x＜1, and 0＜y＜1.In addition, above-mentioned Zn
1-xCd
xS
1-ySe
yAfter the optical excitation of quantum dot by 365 nanometers or 400 nanometers, but really emission wavelength between the white light of 400～700 nanometers.
Though the present invention with preferred embodiment openly as above; right its is not in order to limit the present invention; any those skilled in the art; without departing from the spirit and scope of the present invention; when can doing a little change and retouching, so protection scope of the present invention is when looking being as the criterion that the accompanying Claim book defined.
Claims (20)
1. the preparation method of a white light quanta point, wherein the chemical formula of this white light quanta point is Zn
xCd
1-xA, A=S and composition thereof, 0＜x＜1, and the making method of this white light quanta point comprise:
(a) preparation one sulfur-containing organic solution;
(b) contain cadmium precursor and with one and contain the zinc precursor thing and mix in an organic acid, making a huge legendary turtle compound, and this huge legendary turtle compound is dissolved among the cosolvent, promptly obtain a homogeneous solution; And
(c) mix this sulfur-containing organic solution and this homogeneous solution, can make a Zn
xCd
1-xThe A quantum dot.
2. the preparation method of white light quanta point according to claim 1 is characterized in that, prepares this sulfur-containing organic solution, comprises that the sulphur powder is dissolved in one to be comprised in the organic solvent of vaccenic acid, tri octyl phosphine, tributylphosphine or dioctylamine.
3. the preparation method of white light quanta point according to claim 1, wherein this sulfur-containing organic solution comprises vaccenic acid sulphur solution, tri octyl phosphine sulphur solution, tributylphosphine sulphur solution or dioctylamine sulphur solution.
4. according to the preparation method of the described white light quanta point of claim 2, it is characterized in that, prepare this sulfur-containing organic solution, also be included under 40 ℃～80 ℃, handled 20～40 minutes through a ultrasonic oscillation.
5. the preparation method of white light quanta point according to claim 1 is characterized in that, this contains the cadmium precursor and comprises Cadmium oxide, cadmium acetate or dimethyl cadmium.
6. the preparation method of white light quanta point according to claim 1 is characterized in that, this contains the zinc precursor thing and comprises zinc oxide, zinc acetate, Zinic stearas or zinc ethyl.
7. the preparation method of white light quanta point according to claim 1 is characterized in that, this organic acid comprises fatty acid.
8. the preparation method of white light quanta point according to claim 1 is characterized in that, this organic acid comprises stearic acid, lauric acid or oleic acid.
9. the preparation method of white light quanta point according to claim 1 is characterized in that, this cosolvent comprises phosphine lipid or organic amine.
10. the preparation method of white light quanta point according to claim 9 is characterized in that, this phospholipid comprises trioctyl phosphine oxide.
11. the preparation method of white light quanta point according to claim 9 is characterized in that, this organic amine comprises amino dodecane or cetylamine.
12. the preparation method of white light quanta point according to claim 1 is characterized in that, in the step of this huge legendary turtle compound solution of preparation, also comprises and carries out a whipping step.
13. the preparation method of white light quanta point according to claim 1 is characterized in that, at the range of reaction temperature of (c) step between 250 ℃～350 ℃.
14. the preparation method of white light quanta point according to claim 1 is characterized in that, reaction times of (c) step between between 1 second～120 minute.
15. the preparation method of white light quanta point according to claim 1 is characterized in that, this Zn
xCd
1-xThe particle diameter of A quantum dot is less than 10 nanometers.
16. the preparation method of white light quanta point according to claim 1 is characterized in that, this Zn
xCd
1-xThe A quantum dot is less than or equal to the optical excitation emission wavelength that light excited of 450 nanometers between 400～800 nanometers by an optical excitation wavelength.
17. the preparation method of white light quanta point according to claim 1 is characterized in that, A=S
1-ySe
y, the preparation method of the white light quanta point of 0＜y＜1 before mixing this homogeneous solution and sulfur-containing organic solution, also comprises:
This sulfur-containing organic solution is mixed one contain selenium organic solution, to make a sulfur-bearing and to contain the organic solution of selenium; And
The organic solution of mixing this sulfur-bearing and containing selenium can make Zn in this homogeneous solution
xCd
1-xThe A quantum dot.
18. the preparation method of white light quanta point according to claim 17 is characterized in that, this contains selenium organic solution is by adding selenium powder in the organic solvent of tri octyl phosphine and normal hexane, containing selenium organic solution to prepare this.
19. the preparation method of white light quanta point according to claim 18 is characterized in that, prepares this and contains selenium organic solution, also comprises at room temperature, carries out a ultrasonic oscillation and handles.
20. the preparation method of white light quanta point according to claim 17 is characterized in that, is mixing this sulfur-bearing and is containing the step of the organic solution of selenium in this homogeneous solution, its range of reaction temperature is between 250 ℃～350 ℃.
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